JP7207510B2 - METHOD OF PROCESSING METAL-THERMOPLASTIC FIBER REINFORCED COMPOSITE MEMBER - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a metal-thermoplastic fiber reinforced resin material composite member.

Fiber reinforced plastics (FRP), which are composites of reinforcing fibers (for example, glass fibers, reinforcing fibers, etc.) contained in a matrix resin, are lightweight and excellent in tensile strength, workability, and the like. Therefore, it is widely used from consumer fields to industrial uses. In the automotive industry, the application of FRP to automobile parts is being considered, focusing on the lightness, tensile strength, workability, etc. of FRP, in order to meet the need for vehicle weight reduction that leads to improved fuel efficiency and other performance. .

When FRP itself is used as an automobile member, there are various problems such as the following. First, since FRP has low compressive strength, it is difficult to use it as it is for automobile members that require high compressive strength. Secondly, the FRP matrix resin is generally a thermosetting resin such as an epoxy resin, and is therefore brittle. Third, FRP (in particular, carbon fiber reinforced plastics (CFRP) using reinforcing fibers as reinforcing fibers) is expensive, which causes an increase in the cost of automobile parts. Fourthly, as described above, since the thermosetting resin is used as the matrix resin, it takes a long curing time and the tact time is long. Fifthly, since FRP using a thermosetting resin as a matrix resin does not undergo plastic deformation, it cannot be bent once cured.

In order to solve these problems, recently, a metal member-FRP composite material in which a metal member and FRP are laminated and integrated (composite) has been studied. As for the first problem, the compressive strength of the composite material can be increased by combining a metal member having a high compressive strength with FRP. Regarding the second problem, brittleness is reduced by forming a composite with a metal member having ductility such as steel, so that the composite material can be deformed. As for the third problem, the use of FRP can be reduced by combining low-priced metal members with FRP, so that the cost of automobile members can be reduced.

In order to combine a metal member and FRP, it is necessary to join or bond the metal member and FRP, and as a joining method, generally, a method using an epoxy resin-based thermosetting adhesive is used. Are known.

For example, Patent Literature 1 below proposes a structural material in which a light metal material and CFRP are bonded with an adhesive.

In addition, in the production of metal member-FRP composites, the development of methods that enable production with low energy consumption and low cost is underway.

Patent Document 2 below proposes a method of manufacturing a metal-CFRP composite structure by press-molding a CFRP prepreg made of a reinforcing fiber material and a thermosetting resin material on the surface of a hot-pressed metal material. ing.

WO 1999/10168 JP 2014-100829 A

Although the above Patent Document 1 describes a metal-CFRP structural material in which CFRP is bonded with an adhesive to a metal material that has been processed into a predetermined shape in advance, a method for integrally processing a metal-CFRP structural material is described. is not listed.

In addition, the technique disclosed in Patent Document 2 above requires a bending process such as hot pressing of the metal material before joining the metal member and CFRP, so there is a problem that the manufacturing cost is still high. Furthermore, a metal-CFRP composite structure using a thermosetting resin as the CFRP matrix resin has a problem that delamination is likely to occur at the bonding interface between the metal and the CFRP.

The present invention has been made in view of the above problems, and is a metal-thermoplastic fiber reinforced resin material composite in which a metal member and a fiber reinforced resin material are firmly joined and which can be integrally processed at low cost. The object is to provide a processing method.

In order to solve the above problems, according to one aspect of the present invention, a metal plate having a matrix resin containing a thermoplastic resin and a fiber-reinforced resin material having a reinforcing fiber material disposed on at least one surface thereof is provided as described above. An integral processing step of heating to a predetermined temperature at which the fiber-reinforced resin material alone cannot retain its shape, and then applying a predetermined pressure through a mold having a predetermined shape to integrally process the metal plate. and a mold release step of releasing the fiber reinforced resin material from the mold at a predetermined temperature at which the shape of the fiber reinforced resin material is not completely determined. A processing method is provided.

The thermoplastic resin is a crystalline resin having a melting point Tm, the heating temperature in the integral processing step is a temperature in the temperature range of (Tm−20) to (Tm+10) ° C., and the mold release step is performed. The temperature is preferably in the temperature range of (Tm-30) to (Tm+10)°C.

The thermoplastic resin is an amorphous resin having a glass transition temperature Tg, and the heating temperature in the integral processing step is lower than the decomposition temperature of the amorphous thermoplastic resin, and (Tg + 50) ~ ( Tg + 200) ° C., and the release temperature in the release step is lower than the decomposition temperature of the amorphous thermoplastic resin and is in the temperature range of (Tg + 20) to (Tg + 200) ° C. Temperature is preferred.

The thermoplastic resin is contained in an amount of 20 to 80% by volume with respect to the total volume of the fiber-reinforced resin material, and the total amount of the reinforcing fiber material and the matrix resin is preferably 100% by volume.

The reinforcing fiber material is contained in an amount of 20 to 70% by volume with respect to the total volume of the fiber-reinforced resin material, and the total volume of the reinforcing fiber material and the matrix resin is 100% by volume. preferable.

It is preferable that the metal plate has a thickness of 0.1 to 6.0 mm and a ratio of yield stress to Young's modulus of 0.8×10 ⁻³ or more.

The material of the metal plate is preferably a steel material.

Preferably, the reinforcing fiber material is a carbon fiber material.

It is preferable that the surface of the mold is subjected to a predetermined release treatment.

It is preferable to contain a phenoxy resin as the amorphous thermoplastic resin.

In order to solve the above problems, according to another aspect of the present invention, a metal having a thickness of 0.1 to 6 mm and a ratio of yield stress to Young's modulus of 0.8 × 10 -3 or more a plate, and a fiber reinforced resin material having a thickness of 2 to 12 mm and having a matrix resin containing a thermoplastic resin and a reinforcing fiber material disposed on at least one surface of the metal plate, wherein the fiber reinforced resin The material contains at least 20 to 80% by volume of the thermoplastic resin, and the metal plate and the fiber reinforced resin material are integrally formed into a predetermined shape, a metal-thermoplastic fiber reinforced resin material composite member. provided.

The metal-thermoplastic fiber reinforced resin material composite member according to the present invention is measured by a 90 ° peel adhesion strength test specified in the T-peel test described in JIS K 6854-3, and a width of 15 mm. The peel strength is preferably 20N or more.

In order to solve the above problems, according to another aspect of the present invention, the thickness is 0.1 to 6.0 mm, and the ratio of yield stress to Young's modulus is 0.8 × 10 -3 or more. a metal plate; and a fiber-reinforced resin material having a thickness of 2 to 12 mm and having a matrix resin containing a thermoplastic resin and a reinforcing fiber material disposed on at least one surface of the metal plate, wherein the fiber The reinforced resin material contains at least 20 to 80% by volume of the thermoplastic resin, and the metal plate and the fiber reinforced resin material are integrated to form a predetermined shape.

As described above, according to the present invention, the metal member and the fiber-reinforced resin material have high adhesiveness, and integral processing of the metal-thermoplastic fiber-reinforced resin material composite member is possible.

1 is a schematic diagram showing a cross-sectional structure of a metal-FRP composite member according to a first embodiment of the present invention; FIG. FIG. 4 is a schematic diagram showing another aspect of the cross-sectional structure of the metal-FRP composite member according to the same embodiment. FIG. 4 is an explanatory diagram showing an example of a method for processing the metal-FRP composite member according to the same embodiment; FIG. 4 is a schematic diagram showing a test piece used for a peel strength test of the metal-FRP composite member according to the same embodiment. FIG. 4 is an explanatory view showing an example of another aspect of the processing method of the metal-FRP composite member according to the same embodiment. FIG. 4 is a schematic diagram showing a cross-sectional structure of a metal-FRP composite member according to a second embodiment of the present invention; FIG. 4 is a schematic diagram showing another aspect of the cross-sectional structure of the metal-FRP composite member according to the same embodiment. FIG. 4 is an explanatory diagram showing an example of a method for processing the metal-FRP composite member according to the same embodiment; FIG. 4 is an explanatory view showing an example of another aspect of the processing method of the metal-FRP composite member according to the same embodiment.

Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings. In the present specification and drawings, constituent elements having substantially the same functional configuration are denoted by the same reference numerals, thereby omitting redundant description.

<1. Background>
As explained earlier, in the automotive industry, in order to meet the needs for vehicle body weight reduction, we focused on the lightness, tensile strength, workability, etc. of FRP, for example, automotive parts including frame members such as side sills, pillars, and back doors. Application of FRP to For example, when an automobile receives an impact such as a collision, FRP is affixed to a part of the part that receives the compressive stress, and the FRP breaks preferentially to absorb the impact energy. ing. In addition, it is being studied to improve the strength of the member by using FRP with high tensile strength in the portion that receives tensile stress when the automobile receives an impact.

As the FRP for the automotive member, carbon fiber having both strength and lightness and CFRP formed of a thermosetting resin are generally used as the matrix resin. The inventors of the present invention have found that by applying processing such as bending to a member in which a metal member and FRP using a thermosetting resin are integrated, the FRP breaks and separates from the metal member. In addition, when a metal member and a thermosetting CFRP are hot-pressed to form a composite, when the composite returns to room temperature after processing, the difference between the linear expansion coefficient of the metal member and the linear expansion coefficient of CFRP causes the CFRP to As a result of the compressive stress, it was found that the adhesion surface between the metal member and the CFRP was peeled off. Destruction of CFRP by press load is caused by low bending strength due to low compressive strength of CFRP. It is thought that the reason for this is that the resin at the interface between the FRP and the steel plate sometimes does not follow the contraction of the steel plate and separates from the metal member. Although it is possible to solve the above problem by a method in which the metal member and the CFRP are separately shaped and the CFRP is attached to the shaped metal member using an adhesive, such a method requires the following steps: and the use of adhesives increases manufacturing costs.

In addition, high-strength steel is often used for the automobile members described above in order to reduce the weight of the vehicle body. When a composite of high-strength steel and FRP is pressed, the high-strength steel undergoes deformation (springback) to return to the shape before working after unloading. The inventors have found that this springback causes separation at the interface between the high-strength steel and the FRP.

Therefore, the inventors of the present invention integrally process a metal member and FRP to make a metal-FRP composite member with high product stability. . The present inventors thought that using a thermoplastic resin as the main component of the matrix resin would enable plastic deformation of the FRTP at high temperatures, thereby reducing brittleness and facilitating integral processing. As a result of research based on this idea, the present inventors laminated a metal member and FRTP, and heated the laminate of the metal member and FRTP to a temperature at which the FRTP alone could not maintain its shape. We obtained knowledge that integral processing using a mold is possible. Furthermore, the present inventors released the composite material of the integrally processed metal member and FRTP from the mold at a temperature at which the matrix resin constituting the FRTP can be easily deformed even after integrally processing the laminate. By doing so, it was discovered that interfacial separation between the metal member and FRTP caused by springback can be suppressed.

Then, the inventors of the present invention conducted extensive research, and heated a metal plate having a fiber-reinforced resin material having a matrix resin containing a thermoplastic resin and a fiber-reinforced resin material having a fiber-reinforced material on at least one surface thereof to a predetermined temperature. Thereafter, an integral processing step of applying a predetermined pressure through a mold having a predetermined shape for integral processing, and removing the integrally processed metal plate and fiber reinforced resin material from the mold at a predetermined temperature. Invented a method for processing a metal-thermoplastic fiber reinforced resin material composite member, which includes a mold release step. The present invention laminates a metal member and FRTP, processes the FRTP at a temperature at which the shape cannot be maintained by FRTP alone, and then releases the mold at a temperature at which the shape of FRTP is not completely fixed, thereby integrating the metal member and FRTP. It is possible to process a composite in which the metal member and FRTP are firmly bonded by processing and following the springback of the metal member.

In this embodiment, the heating temperature and release temperature during processing differ depending on whether the thermoplastic resin is a crystalline resin or an amorphous resin. Therefore, hereinafter, embodiments will be described separately for the case where the thermoplastic resin according to the present embodiment is a crystalline resin and the case where the thermoplastic resin is an amorphous resin.

<2. First Embodiment>
<2.1. Structure of metal-fiber reinforced resin material composite>
First, the configuration of a metal-fiber reinforced resin material composite according to a first embodiment of the present invention will be described with reference to FIGS. 1 and 2 are schematic diagrams showing the cross-sectional structure in the stacking direction of a metal-FRTP composite member 1 as a metal-fiber reinforced resin material composite according to this embodiment.

The metal-FRTP composite member 1 is composited with a matrix resin 101 containing a crystalline thermoplastic resin of FRTP12. The metal-FRTP composite member 1 comprises a metal member 11 and an FRTP 12, as shown in FIG. The metal member 11 and the FRTP 12 are compounded by a matrix resin 101 contained in the FRTP 12 . Here, "compositing" means that the metal member 11 and the FRTP 12 are joined together and integrated. Also, "integrated" means that the metal member 11 and the FRTP 12 move as one during processing or deformation.

In this embodiment, the FRTP 12 is provided so as to contact at least one surface of the metal member 11 . However, the FRTP 12 may be provided not only on one side of the metal member 11 but also on both sides. Also, a structure in which a laminate including the FRTP 12 is sandwiched between two metal members 11 may be employed.

Each component and other configurations of the metal-FRTP composite member 1 will be described in detail below.

<2.1.1. Metal member 11>
The material of the metal member 11 is not particularly limited, and examples thereof include iron, titanium, aluminum, magnesium, and alloys thereof. Examples of alloys include iron-based alloys (including stainless steel), Ti-based alloys, Al-based alloys, and Mg alloys. As the metal member according to the present embodiment, it is possible to use a metal material having a large amount of springback, such as high-tensile steel. Excellent effect. The thickness of the metal member 11 is not particularly limited as long as it can be molded by pressing or the like, but is preferably 0.1 to 6.0 mm. If the thickness of the metal member 11 is less than 0.1 mm, it is difficult to obtain sufficient material strength when used as a frame member for an automobile. Also, if the thickness of the metal member 11 is greater than 6.0 mm, the effect of reducing the weight of the automobile body is reduced. Moreover, the shape of the metal member 11 is preferably a thin plate.

In general, the higher the yield stress and the lower the Young's modulus of a material, the greater the amount of springback. The processing method according to the present embodiment obtains a composite material that is integrally processed while maintaining high adhesion to the metal member 11 having a ratio of yield stress to Young's modulus of 0.8 × 10-3 or more. be able to. As described above, the present invention exhibits particularly excellent effects when using the metal member 11 having a large amount of springback. Therefore, the ratio of the yield stress to the Young's modulus of the metal member 11 is more preferably 1.0. ×10 ⁻³ or more, and more preferably 2.0×10 ⁻³ or more.

Any surface treatment may be applied to the steel material that is the material of the metal member 11 . Here, the surface treatment includes, for example, various plating treatments such as zinc plating and aluminum plating, chemical conversion treatments such as chromate treatment and non-chromate treatment, and physical or chemical etching such as sandblasting. Examples include, but are not limited to, roughening treatments. In addition, multiple types of surface treatments may be applied. As the surface treatment, it is preferable that a treatment for the purpose of imparting at least rust resistance is performed.

The surface of the metal member 11 may be treated with a primer in order to enhance adhesion with the FRTP 12 . As a primer used in this treatment, for example, a silane coupling agent or a triazinethiol derivative is preferable. Examples of silane coupling agents include epoxy silane coupling agents, amino silane coupling agents, and imidazole silane compounds. Triazinethiol derivatives include 6-diallylamino-2,4-dithiol-1,3,5-triazine, 6-methoxy-2,4-dithiol-1,3,5-triazine monosodium, 6-propyl-2 ,4-dithiolamino-1,3,5-triazine monosodium and 2,4,6-trithiol-1,3,5-triazine.

<2.1.2. FRTP12>
The FRTP 12 has a matrix resin 101 containing a crystalline thermoplastic resin as a main component, and composite reinforcing fibers 102 contained in the matrix resin 101 . As the FRTP 12, for example, one formed using a prepreg for FRP molding, or a composite in which a matrix resin 101 containing reinforcing fibers 102 is solidified can be used. The FRTP 12 is not limited to one layer, and may have two or more layers as shown in FIG. 2, for example. The thickness of the FRTP 12 and the number of layers n of the FRTP 12 when the FRTP 12 is made up of a plurality of layers may be appropriately set according to the purpose of use. When the FRTP 12 has multiple layers, each layer may have the same configuration or may have a different configuration. Also, the type and content ratio of the reinforcing fibers 102 constituting the FRTP 12 may differ from layer to layer.

(Matrix resin 101)
The metal member 11 and the FRTP 12 are firmly bonded by the matrix resin 101 containing a thermoplastic resin that is a crystalline resin as a main component, and the strongly bonded state is achieved by performing the processing method according to the present embodiment. The metal member 11 and the FRTP 12 can be integrally processed while being held.

A crystalline resin is a resin whose melting point Tm is observed when the melting point is measured using a differential scanning calorimeter (DSC) or differential thermal analysis (DTA). Examples of the crystalline thermoplastic resin contained in the matrix resin 101 include polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polyesters (PEs), nylons, aromatic polyetherketone (PAEK ), polyphenylene sulfide (PPS), polyacetal (POM), modified polyimide, and the like. For example, polyethylene (PE) includes low density polyethylene (LDPE), high density polyethylene (HDPE), ultra high molecular weight polyethylene (UHPE), etc. Polyesters (PEs) include polyethylene terephthalate (PET), Polybutylene terephthalate (PBT) and the like, nylons include 6 nylon (PA6), 6,6-nylon (PA66) and the like, and aromatic polyether ketone (PAEK) includes polyether Ether ketone (PEEK), polyether ether ketone ketone (PEEKK), polyether ketone (PEK) and the like. By containing a crystalline thermoplastic resin in the matrix resin 101, it is possible to solve the problem that the FRP cannot be bent due to its brittleness, which occurs when a thermosetting resin is used.

Further, in order to enhance the adhesiveness between the metal member 11 and the FRTP 12, the matrix resin 101 may contain a crystalline thermoplastic resin whose skeleton and end groups are modified. Acids such as maleic anhydride and carboxylic anhydride can be used to modify the crystalline thermoplastic resin.

The matrix resin 101 may contain, for example, natural rubber, synthetic rubber, elastomer, etc., various inorganic fillers, solvents, pigments, colorants, antioxidants, UV inhibitors, and flame retardants, as long as the adhesion and physical properties of the matrix resin 101 are not impaired. Other additives such as a retardant and a flame retardant auxiliary may be blended. Examples of elastomers that can be used include styrene-based elastomers, olefin-based elastomers, alkene-based elastomers, vinyl chloride-based elastomers, urethane-based elastomers, and amide-based elastomers. The content of the additive is preferably blended so that the total of the content of the thermoplastic resin, the content of the reinforcing fibers 102 and the content of the additive is 100% by volume.

The content of the thermoplastic resin contained in the matrix resin 101 is preferably 20% by volume or more and 80% by volume or less with respect to the total volume of the FRTP 12 . If the content of the thermoplastic resin is less than 20% by volume, the thermocompression bonding between the metal member 11 and the FRTP 12 will be insufficient, and there is a possibility that they will separate at the bonding surface. On the other hand, if the content of the thermoplastic resin exceeds 80% by volume, the softened and melted resin flows out into the mold during press working, promoting voids and defects in the carbon fiber reinforced thermoplastic (CFRTP). A problem may arise in that the strength of the composite decreases. More preferably, the content of the thermoplastic resin contained in the matrix resin 101 is 35% by volume or more and 75% by volume or less. The matrix resin 101 is preferably contained such that the sum of the content of the matrix resin 101 and the content of the reinforcing fibers 102 is 100% by volume.

(Reinforcement fiber 102)
Although the reinforcing fibers 102 are not particularly limited, carbon fibers, boron fibers, silicon carbide fibers, glass fibers, aramid fibers, etc. are preferable, and carbon fibers are more preferable from the viewpoint of weight reduction. As for the type of carbon fiber, for example, both PAN-based and pitch-based carbon fibers can be used, and can be selected according to the purpose and application. Moreover, as the reinforcing fiber 102, one type of the above fibers may be used alone, or a plurality of types may be used in combination.

In the FRP used for the FRTP 12, the reinforcing fiber base material, which is the base material of the reinforcing fiber 102, includes, for example, a non-woven fabric base material using chopped fibers, a cloth material using continuous fibers, a unidirectional reinforcing fiber base material (UD material ), short fiber substrates, etc. can be used. From the viewpoint of the reinforcing effect, it is preferable to use a cloth material or a UD material as the reinforcing fiber base material.

(fiber density)
The fiber density (VF: Volume Fraction) of FRTP12 is a factor that affects strength, and generally, the higher the VF, the higher the strength of FRTP12. In this embodiment, it is preferable that the reinforcing fibers 102 are contained in an amount of 20 to 70% by volume with respect to the total volume of the FRTP 12 . When continuous fibers are used as the reinforcing fibers 102, the VF of the FRTP 12 is preferably 40% by volume or more and 70% by volume or less. If the VF of the reinforcing fibers 102 using continuous fibers exceeds 70% by volume, it becomes difficult to produce the FRTP 12 with high orientation. In addition, if the VF of the reinforcing fibers 102 when using continuous fibers is less than 40% by volume, the reinforcing fibers 102 are difficult to orient in the resin in the process of heat curing, so the strength peculiar to continuous fibers cannot be obtained. There is If the VF is too large, voids and defects are likely to occur in the FRTP 12, making it difficult to obtain a high strength. The following are more preferable.

Moreover, when the fibers used as the reinforcing fibers 102 are short fibers, the content is preferably 20% by volume or more and 50% by volume or less. If the VF of the reinforcing fibers 102 using short fibers exceeds 50% by volume, it becomes difficult to produce the FRTP 12 with high orientation. Further, if the VF of the reinforcing fibers 102 using short fibers is less than 20% by volume, sufficient strength as a strength member may not be obtained. More preferably, the VF of the FRTP 12 when short fibers are used as the reinforcing fibers 102 is 25% by volume or more and 45% by volume or less. The short fibers refer to fibers having a length of 0.1 mm to 12 mm.

In the metal-FRTP composite member 1 according to this embodiment, the FRTP 12 is formed using at least one prepreg for CFRTP molding. The FRTP 12 is not limited to one layer, and may have two or more layers as shown in FIG. 3, for example. The thickness of the FRTP 12 and the number of layers n of the FRTP 12 when the FRTP 12 is made up of a plurality of layers may be appropriately set according to the purpose of use. When the FRTP 12 has multiple layers, each layer may have the same configuration or may have a different configuration. Also, the type and content ratio of the reinforcing fibers 102 constituting the FRTP 12 may differ from layer to layer.

<2.2. Processing method of metal-FRTP composite member 1>
The structure of the metal-FRTP composite member 1 as the metal-fiber reinforced resin material composite according to the present embodiment has been described above in detail. Next, a method for processing the metal-FRTP composite member 1 according to this embodiment will be described with reference to FIGS. 3 and 4 are explanatory diagrams showing examples of processing steps for the metal-FRTP composite member 1. FIG.

The metal-FRTP composite member 1 is integrally processed by heating the FRTP 12 and the metal member 11 having a predetermined shape to a predetermined heating temperature and then applying a predetermined pressure through a mold having a predetermined shape. and a releasing step of releasing the metal member 11 and the FRTP 12 thus integrated from the mold at a predetermined temperature. Integral processing in the present invention means bonding the FRTP 12 and the metal member 11 with the matrix resin 101 and processing them without separating the metal member 11 and the FRTP 12 . A method of combining (integrating) the metal member 11 and the FRTP 12 by thermocompression bonding will be described below.

<2.2.1. Method 1>
First, as shown in FIG. 3A, the FRTP 12 is arranged on at least one surface of the metal member 11 and laminated to form a laminate. In FIG. 3, a mold having a convex shape is defined as an upper mold m1, and a mold having a concave shape is defined as a lower mold m2. showing. At this time, the bonding surface of the FRTP 12 to be bonded to the metal member is preferably roughened by blasting or the like, or activated by plasma treatment, corona treatment, or the like. In addition, it is preferable to preliminarily remove deposits on the surface of the metal member 11 and degrease it. Removal of such deposits and degreasing can be performed by known techniques.

In FIG. 3(a), instead of the FRTP 12, it is also possible to integrally process the FRP molding prepreg and the metal member 11 while compositing them at the time of integral processing, which will be described later, in place of the FRTP 12. be. It is also possible to integrally process a composite of the metal member 11 and the FRTP 12 in advance by a method to be described later. Further, the FRTP 12 is not limited to one layer as shown in FIG. 2, and may be multiple layers.

Next, the laminate of this metal member 11 and FRTP 12 is heated to a predetermined heating temperature T1 (FIG. 2(b)). The heating temperature T1 is the temperature at which the FRTP itself deforms due to its own weight if it is kept at that temperature for a long time, for example, one hour or more, that is, it cannot retain its shape by itself. Specifically, the heating temperature T1 is a temperature within the range of (Tm−20)° C. or higher and (Tm+10)° C. or lower, where Tm is the melting point of the thermoplastic resin contained in the matrix resin 101 of the FRP. is preferred. If the heating temperature T1 is less than (Tm−20)° C., the possibility of separation at the interface between the metal member 11 and the FRTP 12 increases. In addition, when the heating temperature T1 is less than (Tm-20) ° C., the flowability of the matrix resin 101 is low. is more likely to occur. If the heating temperature T1 exceeds (Tm+10)° C., the fluidity of the matrix resin 101 becomes too high, causing the matrix resin 101 to flow out of the mold m, and the content of the matrix resin 101 with respect to the total volume of the FRTP 12 decreases. and the strength of the composite is likely to decrease. As the content of the matrix resin 101 decreases, voids are likely to occur in the FRTP 12, and the strength of the FRTP 12 may decrease. In addition, as the content of the thermoplastic resin contained in the matrix resin 101 with respect to the total volume of the FRTP 12 decreases, the adhesive strength between the metal member 11 and the FRTP 12 decreases and peeling is promoted, resulting in a decrease in strength. There is The heating temperature T1 is more preferably (Tm-10)°C or higher and (Tm+0)°C or lower.

In order to improve the releasability of the metal-FRTP composite member 1, the surface of the mold m is preferably subjected to release treatment. The release treatment method is not particularly limited, and examples thereof include release agent application, surface modification of the mold m, and film formation. Release agents mainly composed of silicone, mineral water, ester, etc. can be used as appropriate. can be used

Also, the mold m is preferably preheated. Preheating of the mold m is not particularly limited, and can be performed, for example, by combustion heating using a gas burner, infrared heating, high-frequency dielectric heating, or the like. By preheating the mold m, the time required for the laminate of the metal member 11 and the FRTP 12 to reach a predetermined temperature can be shortened, and production efficiency can be improved.

Next, as shown in FIG. 3(c), a metal mold m is used to apply a predetermined pressure to the metal member 11 and the FRTP 12, and the metal member 11 and the FRTP 12 are integrated at the above heating temperature T1 to be processed into a predetermined shape. conduct.

The press load during processing is preferably 0.1 kN or more and 100 kN or less. If it is less than 0.1 kN, it may not be possible to process the FRTP 12 having a thickness of less than 12 mm and the composite material of the steel plate having a thickness of 0.1 mm or more into a predetermined shape. On the other hand, if the press load is 100 kN, the fibers may break, which is not preferable.

The working speed of the laminate of the metal member 11 and FRP is defined by the strain rate of the material, and its range is preferably 0.05 to 10 s-1. The strain rate of the material is the velocity of the mold m divided by the thickness of the material. If the strain rate is less than 0.05 s-1, integral molding is possible, but the productivity is remarkably lowered. If it exceeds 10s-1, the resin in the FRTP 12 cannot follow the processing of the steel sheet, and there is a possibility that the layers of the FRTP 12 will be misaligned. More preferably, the processing speed is within a range where the strain rate of the laminate of the metal member 11 and FRP is 0.5 s ⁻¹ or more and 5 s ⁻¹ or less.

If the pressing time is at least 1 minute or more, the resin in the FRTP moves to the steel plate and the adhesiveness is secured, so the integrated metal-FRTP composite member 1 can be processed, and it is 5 minutes or more. and preferred. Although there is no particular upper limit, it is preferably 10 minutes or less from the viewpoint of productivity.

Thereafter, as shown in FIG. 3(d), the pressure applied by the mold m is removed at the mold release temperature T2, and the metal-FRTP composite member 1 is obtained by removing it from the mold m.

At this time, the release temperature T2 is set so that when the FRTP alone is held at the above temperature, a minute force, for example, a force of 1 N or more is applied, so that the carbon fibers and resin in the FRTP do not crack. It is the temperature at which the shape is not fixed. Specifically, the heating temperature T2 is preferably a temperature within the range of (Tm-30)°C to (Tm+10)°C. If the release temperature T2 is less than (Tm-30)° C., the FRTP 12 cannot follow the springback of the metal member 11, and separation may occur at the interface between the metal member 11 and the FRTP 12. If the release temperature T2 is higher _than (Tm+10)° C., the fluidity of the matrix resin 101 becomes too high, and the matrix resin 101 may flow out of the mold m. As a result, the matrix resin in FRTP12 is reduced, and the strength of the composite may be lowered. The release temperature T2 is _more preferably (Tm-20)°C or higher and (Tm+0)°C or lower.

If the release temperature T2 is within the above temperature range, the resin in the FRTP ₁₂ has fluidity that can follow the springback of the metal member 11, so the pressure removal rate from the metal-FRTP composite member 1 is No special restrictions.

The peel strength between the metal member 11 and the FRTP 12 can be measured by the method specified in "JIS K 6854-3 Adhesive-Peel Adhesion Strength Test Method-Part 3: T-type Peel". FIG. 4 shows a test piece 2 used for the peel strength test. Specifically, a test piece having a width of 15 mm and a length of 90 mm is cut out from the metal-FRTP composite member 1 after processing, with the metal member 11 joined to both surfaces of the FRTP 12 . The metal member 11 of the cut test piece is peeled off from the FRTP 12 by 30 mm, and only the metal portion is bent at 90 degrees. The metal part bent at 90 degrees is gripped with a chuck and set in a peel tester, and the peel strength test is performed with the crosshead speed of the peel tester set at 300 mm/min. The obtained maximum load is taken as the peel strength. Also, for a metal-FRTP composite member in which the metal member 11 is bonded to only one surface of the FRTP 12 and integrally processed, a test piece can be prepared by the following method and a peel strength test can be performed. A composite member having a width of 15 mm and a length of 90 mm is cut from the metal-FRTP composite member, the metal member 11 of the cut composite member is peeled off from the FRTP 12 by 30 mm, and the peeled metal portion is bent at 90 degrees. On the surface of the FRTP 12 opposite to the surface to which the metal member 11 is bonded, a room temperature curing adhesive is used to bond a metal member bent at 90 degrees. A test piece prepared as described above can be set in a peel tester in the same manner as described above and used for a peel strength test. In addition, when the adhesive strength between the room temperature curing adhesive used and the FRTP 12 was separately examined, it was 200 N or more, so the peel strength test result reflects the peel strength between the metal member 11 and the FRTP 12. becomes.

Although the case where the FRTP 12 is laminated on the metal member 11 has been described above, it is also possible to laminate the metal member 11 on the FRTP 12 and process it, as shown in FIG. A method of laminating the metal member 11 on the upper portion of the FRTP 12 and integrally processing the same will be described below with reference to FIG.

<2.2.2. Method 2>
When the metal member 11 is laminated on the upper part of the FRTP 12 and integrally processed, as shown in FIG. It is placed on the support plate b, and pressure is applied through the mold m for thermocompression bonding.

As in Method 1, the bonding surface of the FRTP 12 to be bonded to the metal member 11 is preferably roughened by blasting or activated by plasma or corona treatment, for example. In FIG. 5(a), instead of the FRTP 12, a prepreg for FRP molding can be laminated. Further, the FRTP 12 is not limited to one layer as shown in FIG. 2, and may be multiple layers.

Next, as shown in FIG. 5(b), the laminate of the FRTP 12 and the metal member 11 is placed on the support plate b and heated to _a predetermined heating temperature T1. _The heating temperature T1 at this time is the same as the heating temperature T1 of method ₁ .

In order to improve the releasability of the metal-FRTP composite member 1, the surface of the mold m is preferably subjected to the same release treatment as in method 1. Moreover, it is preferable that the surface of the support plate b is also subjected to a release treatment similar to that of Method 1. Moreover, when heating the laminate, it is preferable to preheat the mold m by the same method as method 1.

Next, as shown in FIG. 5(c), a metal mold m is used to apply pressure to the metal member 11, the molded body of the FRTP 12, and the support plate b, and the metal member 11 and the support plate b are processed into a predetermined shape at the above heating temperature T1. . At this time, it is preferable that the shape of the mold m takes into consideration the thickness of the support plate b and the like so that the laminate of the metal member 11 and the FRTP 12 can be the metal-FRTP composite member 1 of a desired shape.

The press load, processing speed, pressure application time, etc. can be set to the same conditions as in Method 1.

After that, as shown in FIG. 5(d), the pressure from the mold m is removed at the mold release temperature T2, and the metal _- FRTP composite member 1 is obtained by removing it from the mold m. The mold release temperature T2 at this _time is the same as the mold release temperature T2 in the _first method.

In this embodiment, the FRTP 12 is provided so as to contact at least one surface of the metal member 11, but the FRTP 12 is provided not only on one side of the metal member 11, but also on both sides. may be provided in each. When the FRTP 12 is provided on both sides of the metal member 11, it is possible to process by applying method 2 above. Also, a structure in which a laminate including the FRTP 12 is sandwiched between two metal members 11 may be employed.

According to the present embodiment described above, the metal-FRTP composite member 1 in which the metal member 11 and the FRTP 12 are firmly bonded without the step of bonding the metal member 11 and the FRTP 12 in advance or the step of shaping is required. Integrated processing becomes possible. In this method, the metal member 11 and the FRTP 12 may be pre-bonded and then integrally processed in the next step.

<3. Second Embodiment>
<3.1. Structure of metal-fiber reinforced resin material composite>
A metal-fiber reinforced resin material composite according to the second embodiment of the present invention contains an amorphous thermoplastic resin as a matrix resin 101A and is composited. The configuration of a metal-fiber reinforced resin material composite according to a second embodiment of the present invention will be described with reference to FIGS.

The metal-FRTP composite member 1A is composited with a matrix resin 101A containing an amorphous thermoplastic resin of FRTP 12A. The metal-FRTP composite member 1A, as shown in FIG. 6, comprises a metal member 11 and FRTP 12A. The metal member 11 and the FRTP 12A are combined with a matrix resin 101A included in the FRTP 12A.

In this embodiment, the FRTP 12A is provided so as to be in contact with at least one surface of the metal member 11 . However, the FRTP 12A may be provided not only on one side of the metal member 11, but also on both sides. Also, a structure may be adopted in which a laminate including the FRTP 12A is sandwiched between two metal members 11. FIG.

Each component and other configurations of the metal-FRTP composite member 1A will be described in detail below. Since the metal member 11 according to this embodiment is the same as that of the first embodiment, detailed description thereof is omitted here.

<3.1.1. FRTP12A>
The FRTP 12A has a matrix resin 101A containing an amorphous thermoplastic resin and composite reinforcing fibers 102 contained in the matrix resin 101A. As the FRTP 12A, as in Method 1, for example, one formed using a prepreg for FRP molding or a composite in which the matrix resin 101A containing the reinforcing fibers 102 is solidified can be used, and the number of layers is not limited to one. , for example, as shown in FIG. 7, it may be two or more layers.

(Matrix resin 101A)
The metal member 11 and the FRTP 12A are firmly bonded by the matrix resin 101A containing a thermoplastic resin that is a crystalline resin as a main component, and the strongly bonded state is achieved by performing the processing method according to the present embodiment. The metal member 11 and the FRTP 12A can be integrally processed while being held.

An amorphous resin is a resin in which no exothermic peak due to crystallization is observed and only the glass transition point Tg is observed when the melting point is measured using a differential scanning calorimeter or differential thermal analysis. be. Examples of the amorphous resin contained in the matrix resin 101A include phenoxy resin, polymethylmethacrylate (PMMA), polystyrene (PS), polycarbonate (PC), amorphous polyarylate (PAR), polysulfone (PSU), and the like. mentioned. By containing a crystalline thermoplastic resin in the matrix resin 101, it is possible to solve the problem that the FRP cannot be bent due to its brittleness, which occurs when a thermosetting resin is used.

When carbon fibers are used as the reinforcing fibers 102A, the matrix resin 101A preferably contains a phenoxy resin from the viewpoint of adhesion to the metal member 11 and affinity with the surface of the carbon fibers. Preference is given to using phenoxy resins. A "phenoxy resin" is a linear polymer obtained from a condensation reaction between a dihydric phenol compound and epihalohydrin, or a polyaddition reaction between a dihydric phenol compound and a bifunctional epoxy resin, and is an amorphous thermoplastic resin. is. A phenoxy resin can be obtained by a conventionally known method in a solution or without a solvent, and can be used in any form of powder, varnish and film.

Since the phenoxy resin has a molecular structure very similar to that of the epoxy resin, the phenoxy resin has heat resistance equivalent to that of the epoxy resin, and also has good adhesiveness to the metal member 11 . Furthermore, a so-called partially cured resin can be obtained by adding a curing component such as an epoxy resin to the phenoxy resin and copolymerizing the resin. By using such a partially cured resin as the matrix resin 101A, it is possible to obtain a matrix resin having excellent impregnating properties into the reinforcing fibers 102 . Furthermore, by thermally curing the curing component in this partially cured resin, it is possible to prevent the matrix resin 101A in the FRTP 12A from melting or softening when exposed to high temperatures, unlike normal thermoplastic resins. The amount of the curing component to be added to the phenoxy resin may be appropriately determined in consideration of the impregnating properties of the reinforcing fibers 102, the brittleness of the FRTP 12A, the tact time, the workability, and the like. By using the phenoxy resin as the matrix resin 101A in this way, it is possible to add and control the curing component with a high degree of freedom.

For example, the surfaces of the reinforcing fibers 102 are often coated with a sizing agent that is compatible with epoxy resin. Since the structure of phenoxy resin is very similar to that of epoxy resin, the sizing agent for epoxy resin can be used as it is by using phenoxy resin as the matrix resin 101A. Therefore, cost competitiveness can be enhanced.

In addition, among thermoplastic resins, phenoxy resin has good moldability and excellent adhesiveness with the reinforcing fiber 102. In addition, by using acid anhydrides, isocyanate compounds, caprolactam, etc. as cross-linking agents, high heat resistance can be obtained after molding. It is also possible to impart properties similar to those of a curable thermosetting resin. Therefore, in the present embodiment, it is preferable to use, as the resin component of the matrix resin 101A, a solidified or cured resin composition containing 50 parts by mass or more of the phenoxy resin with respect to 100 parts by mass of the resin component. By using such a resin composition, it becomes possible to firmly join the metal member 11 and the FRTP 12A. More preferably, the resin composition contains 55 parts by mass or more of the phenoxy resin in 100 parts by mass of the resin component. The form of the adhesive resin composition can be, for example, powder, liquid such as varnish, or solid such as film. The term "solidified product" simply means that the resin component itself is solidified, and the term "cured product" means that the resin component is cured by adding various curing agents. . The curing agent that can be contained in the cured product includes a cross-linking agent as described later, and the above-mentioned "cured material" includes the cross-linked cured product.

The content of the phenoxy resin can be measured using infrared spectroscopy (IR: InfraRed spectroscopy) as follows, and the content of the phenoxy resin is determined from the target resin composition by infrared spectroscopy. When analyzing, it can be measured by using a general method of infrared spectroscopic analysis such as transmission method or ATR reflection method.

The FRTP 12A is scraped off with a sharp knife or the like, fibers are removed as much as possible with tweezers or the like, and the resin composition to be analyzed is sampled from the FRTP 12A. In the transmission method, the KBr powder and the resin composition powder to be analyzed are uniformly mixed and crushed in a mortar or the like to form a thin film, which is used as a sample. In the case of the ATR reflection method, as in the transmission method, powders may be uniformly mixed and crushed in a mortar to prepare a tablet to prepare a sample. The surface of 8 mm) may be scratched with a file or the like, and the powder of the resin composition to be analyzed may be sprinkled and adhered to form a sample. In any method, it is important to measure the background of KBr alone before mixing with the resin to be analyzed. As the IR measurement device, a commercially available general one can be used, and the analysis accuracy is such that the absorbance can be distinguished in units of 1% and the wavenumber can be distinguished in units of 1 cm. Apparatus is preferable, and examples thereof include FT/IR-6300 manufactured by JASCO Corporation.

When investigating the content of the phenoxy resin, the absorption peaks of the phenoxy resin are present, for example, at 1450 to 1480 cm-1, around 1500 cm-1, around 1600 cm-1, and the like. Therefore, the content of the phenoxy resin is calculated based on the previously prepared calibration curve showing the relationship between the absorption peak intensity and the phenoxy resin content, and the measured absorption peak intensity. It is possible to

The average molecular weight of the phenoxy resin is, for example, in the range of 10,000 or more and 200,000 or less, preferably 20,000 or more and 100,000 or less, more preferably in the range of 10,000 or more and 200,000 or less as a weight average molecular weight (Mw). is in the range of 30,000 to 80,000. By setting the Mw of the phenoxy resin within the range of 10,000 or more, the strength of the molded body can be increased. increase. On the other hand, by setting the Mw of the phenoxy resin to 200,000 or less, the workability and processability can be excellent, and this effect is achieved by setting the Mw to 100,000 or less, further 80,000 or less. And even higher.

The hydroxyl equivalent (g/eq) of the phenoxy resin used in the present embodiment is, for example, within the range of 50 or more and 1000 or less, preferably 50 or more and 750 or less, more preferably 50 or more and 500 or less. Within range. By setting the hydroxyl equivalent weight of the phenoxy resin to 50 or more, the number of hydroxyl groups is reduced, which lowers the water absorption rate, so that the mechanical properties of the cured product can be improved. On the other hand, by setting the hydroxyl equivalent of the phenoxy resin to 1000 or less, it is possible to suppress the decrease in the number of hydroxyl groups, thereby improving the mechanical properties of the metal-FRTP composite member 1A. This effect is further enhanced by setting the hydroxyl equivalent to 750 or less, further 500 or less.

The phenoxy resin is not particularly limited as long as it satisfies the above physical properties, but preferred are bisphenol A type phenoxy resins (for example, Nippon Steel & Sumikin Chemical Co., Ltd. Phenotote YP-50, Phenotote YP-50S, available as Phenotote YP-55U), bisphenol F type phenoxy resin (for example, available as Phenotote FX-316 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), copolymerized phenoxy resin of bisphenol A and bisphenol F (for example, Nippon Steel & Sumitomo Metal YP-70 manufactured by Kagaku Co., Ltd.), brominated phenoxy resins other than the phenoxy resins listed above, phosphorus-containing phenoxy resins, special phenoxy resins such as sulfone group-containing phenoxy resins (for example, phenoxy resins manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Tote YPB-43C, Phenotote FX293, YPS-007, etc.). These resins can be used individually by 1 type or in mixture of 2 or more types.

◇Crosslinkable resin composition A resin composition containing a phenoxy resin (hereinafter also referred to as “phenoxy resin (A)”) is mixed with, for example, an acid anhydride, isocyanate, caprolactam, etc. as a crosslinking agent to achieve crosslinking. It can also be a flexible resin composition (that is, a cured product of a resin composition). Since the crosslinkable resin composition is crosslinked using the secondary hydroxyl groups contained in the phenoxy resin (A), the heat resistance of the resin composition is improved. It is advantageous for application. For cross-linking using the secondary hydroxyl groups of the phenoxy resin (A), it is preferable to use a cross-linkable resin composition in which the cross-linkable curable resin (B) and the cross-linking agent (C) are blended. As the cross-linkable curable resin (B), for example, an epoxy resin or the like can be used, but it is not particularly limited. By using such a crosslinkable resin composition, a second cured product (crosslinked cured product) having a glass transition point Tg greatly improved as compared with the case of using the phenoxy resin (A) alone can be obtained. be done. The glass transition point Tg of the crosslinked cured product of the crosslinkable resin composition is, for example, 160° C. or higher, preferably in the range of 170° C. or higher and 220° C. or lower.

In the crosslinkable resin composition, as the crosslinkable curable resin (B) to be blended with the phenoxy resin (A), an epoxy resin having two or more functionalities is preferred. Bifunctional or more functional epoxy resins include bisphenol A type epoxy resins (for example, available as Epotote YD-011, Epotote YD-7011, Epotote YD-900 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), bisphenol F type epoxy resins (eg , Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YDF-2001), diphenyl ether type epoxy resin (for example, Nippon Steel & Sumikin Chemical Co., Ltd. available as YSLV-80DE), tetramethylbisphenol F type epoxy resin (for example, Nippon Steel & Sumikin Chemical available as YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), bisphenol sulfide type epoxy resin (for example, available as YSLV-120TE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), hydroquinone type epoxy resin (for example, Epotote YDC-1312 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) available as), phenol novolac type epoxy resin, (for example, available as Epotote YDPN-638 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), ortho-cresol novolac type epoxy resin (for example, available as Epotote YDCN-701, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) YDCN-702, Epotohte YDCN-703, Epotohte YDCN-704), aralkylnaphthalenediol novolac type epoxy resin (e.g. available as ESN-355 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), triphenylmethane type epoxy resin (e.g. , available as EPPN-502H manufactured by Nippon Kayaku Co., Ltd.) and the like, but are not limited to these. Moreover, these epoxy resins may be used individually by 1 type, and may be used in mixture of 2 or more types.

The cross-linking curable resin (B) is not particularly limited, but is preferably a crystalline epoxy resin having a melting point of 70° C. or higher and 145° C. or lower and a melt viscosity at 150° C. of 2.0 Pa·. s or less is more preferable. By using a crystalline epoxy resin exhibiting such melting characteristics, the melt viscosity of the crosslinkable resin composition as a resin composition can be reduced, and the adhesiveness of FRTP12A can be improved. If the melt viscosity exceeds 2.0 Pa·s, the moldability of the crosslinkable resin composition may deteriorate, and the homogeneity of the metal-FRTP composite member 1A may deteriorate.

Examples of crystalline epoxy resins suitable as the cross-linkable curable resin (B) include Epotote YSLV-80XY, YSLV-70XY, YSLV-120TE, YDC-1312 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and YX-4000 manufactured by Mitsubishi Chemical Corporation. , YX-4000H, YX-8800, YL-6121H, YL-6640, etc.; HP-4032, HP-4032D, HP-4700, etc. manufactured by DIC Corporation; NC-3000, etc. manufactured by Nippon Kayaku Co., Ltd.;

The cross-linking agent (C) three-dimensionally cross-links the phenoxy resin (A) by forming an ester bond with the secondary hydroxyl group of the phenoxy resin (A). Therefore, unlike strong cross-linking such as curing of thermosetting resin, the cross-linking can be broken by hydrolysis reaction, so that the metal member 11 and the FRTP 12A can be easily separated.

Acid anhydrides are preferred as the cross-linking agent (C). The acid anhydride is not particularly limited as long as it is solid at normal temperature and does not have much sublimation, but from the viewpoint of imparting heat resistance to the metal-FRTP composite member 1A and reactivity, phenoxy resin ( A) aromatic acid anhydrides having two or more acid anhydrides that react with hydroxyl groups are preferred. In particular, an aromatic compound having two acid anhydride groups, such as pyromellitic anhydride, has a higher cross-linking density than a combination of trimellitic anhydride and a hydroxyl group, which improves heat resistance, so it is preferably used. be done. Aromatic acid dianhydrides such as phenoxy resins such as 4,4'-oxydiphthalic acid, ethylene glycol bis-anhydrotrimellitate, and 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride and an aromatic acid dianhydride having compatibility with the epoxy resin is more preferable because it has a large effect of improving the glass transition point Tg. In particular, aromatic acid dianhydrides having two acid anhydride groups, such as pyromellitic anhydride, have improved crosslinking density compared to, for example, phthalic anhydride having only one acid anhydride group, Since heat resistance is improved, it is preferably used. That is, the aromatic acid dianhydride has good reactivity because it has two acid anhydride groups, and a crosslinked cured product having sufficient strength for demolding can be obtained in a short molding time, and the phenoxy resin (A) The esterification reaction with the secondary hydroxyl group inside generates four carboxyl groups, so the final crosslink density can be increased.

The reaction of the phenoxy resin (A), the epoxy resin as the cross-linking curable resin (B), and the cross-linking agent (C) is a secondary hydroxyl group in the phenoxy resin (A) and the acid anhydride group of the cross-linking agent (C). and the reaction of the carboxyl groups generated by this esterification reaction with the epoxy groups of the epoxy resin to crosslink and cure. A phenoxy resin crosslinked product can be obtained by the reaction of the phenoxy resin (A) and the crosslinker (C). It exhibits excellent properties such as improved impregnation, acceleration of cross-linking reaction, improved cross-linking density, and improved mechanical strength.

In the crosslinkable resin composition, although the epoxy resin as the crosslinkable curable resin (B) coexists, the main component is the phenoxy resin (A), which is a thermoplastic resin, and its secondary hydroxyl group and It is believed that the esterification reaction with the acid anhydride group of the cross-linking agent (C) is preferential. That is, since the reaction between the acid anhydride used as the cross-linking agent (C) and the epoxy resin used as the cross-linking curable resin (B) takes time (reaction rate is slow), the cross-linking agent (C) The reaction with the secondary hydroxyl group of the phenoxy resin (A) occurs first, and then the cross-linking agent (C) remaining in the previous reaction or the remaining carboxyl group derived from the cross-linking agent (C) reacts with the epoxy resin. This further increases the crosslink density. Therefore, unlike a resin composition containing an epoxy resin, which is a thermosetting resin, as a main component, the crosslinked cured product obtained from the crosslinkable resin composition is a thermoplastic resin and has excellent storage stability.

In the crosslinkable resin composition utilizing crosslinking of the phenoxy resin (A), the crosslinkable curable resin (B) is in the range of 5 parts by mass or more and 85 parts by mass or less with respect to 100 parts by mass of the phenoxy resin (A). It is preferably contained so that The content of the crosslinked curable resin (B) relative to 100 parts by mass of the phenoxy resin (A) is more preferably in the range of 9 parts by mass or more and 83 parts by mass or less, and still more preferably 10 parts by mass or more and 80 parts by mass or less. Within range. By setting the content of the crosslinked curable resin (B) to 85 parts by mass or less, the curing time of the crosslinked curable resin (B) can be shortened. The recyclability of FRTP12A is improved. This effect is further enhanced by setting the content of the cross-linking curable resin (B) to 83 parts by mass or less, further 80 parts by mass or less. On the other hand, by setting the content of the cross-linking curable resin (B) to 5 parts by mass or more, it becomes easier to obtain the effect of improving the cross-linking density by adding the cross-linking curable resin (B), and the cross-linking curing of the cross-linkable resin composition It becomes easier for the product to develop a glass transition point Tg of 160° C. or higher, and fluidity is improved. Here, the crosslinkable resin composition contains 20 to 80% by volume of the phenoxy resin (A) relative to the total volume of FRTP12A, and 20 to 70% by volume of the reinforcing fiber 102 relative to the total volume of FRTP12A. In the range, it is preferably contained so as to satisfy the ratio of the phenoxy resin (A) and the crosslinkable resin composition described above. The content of the cross-linking curable resin (B) is determined by similarly measuring the peak derived from the epoxy resin by the method using infrared spectroscopy as described above. You can measure quantity.

The amount of the cross-linking agent (C) is usually in the range of 0.6 mol or more and 1.3 mol or less of the acid anhydride group per 1 mol of the secondary hydroxyl group of the phenoxy resin (A), preferably The amount is in the range of 0.7 mol or more and 1.3 mol or less, more preferably in the range of 1.1 mol or more and 1.3 mol or less. When the amount of the acid anhydride group is 0.6 mol or more, the crosslink density is high, resulting in excellent mechanical properties and heat resistance. This effect is further enhanced by setting the amount of the acid anhydride group to 0.7 mol or more, further 1.1 mol or more. When the amount of acid anhydride groups is 1.3 mol or less, it is possible to prevent unreacted acid anhydrides and carboxyl groups from adversely affecting curing properties and crosslink density. Therefore, it is preferable to adjust the blending amount of the cross-linking curable resin (B) according to the blending amount of the cross-linking agent (C). Specifically, for example, the epoxy resin used as the cross-linking curable resin (B) reacts the carboxyl groups generated by the reaction between the secondary hydroxyl groups of the phenoxy resin (A) and the acid anhydride groups of the cross-linking agent (C). For this purpose, the amount of the epoxy resin compounded should be within the range of 0.5 mol or more and 1.2 mol or less in terms of equivalent ratio to the cross-linking agent (C). Preferably, the equivalent ratio of the cross-linking agent (C) to the epoxy resin is within the range of 0.7 mol or more and 1.0 mol or less.

A crosslinkable resin composition can be obtained by blending the crosslinker (C) together with the phenoxy resin (A) and the crosslinkable curable resin (B). (D) may be further contained. The accelerator (D) is not particularly limited as long as it is solid at room temperature and does not sublimate. Examples include tertiary amines such as triethylenediamine, 2-methylimidazole, 2-phenylimidazole, Examples include imidazoles such as 2-phenyl-4-methylimidazole, organic phosphines such as triphenylphosphine, and tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate. These accelerators (D) may be used alone or in combination of two or more. When forming the matrix resin 101A by making the crosslinkable resin composition fine powder and adhering it to the reinforcing fiber base material using a powder coating method using an electrostatic field, the promoter (D) is used as the catalyst activation temperature. It is preferable to use an imidazole-based latent catalyst that is solid at room temperature of 130° C. or higher. When the accelerator (D) is used, the amount of the accelerator (D) is 0 with respect to 100 parts by mass of the total amount of the phenoxy resin (A), the cross-linking curable resin (B) and the cross-linking agent (C). .It is preferable to make it within the range of 1 part by weight or more and 5 parts by weight or less.

The crosslinkable resin composition is solid at room temperature, and its melt viscosity is 3,000 Pa s or less, which is the lower limit of the melt viscosity in the temperature range of 160 to 250 ° C. It is preferably 2,900 Pa·s or less, more preferably 2,800 Pa·s or less. By setting the minimum melt viscosity in the temperature range of 160 to 250° C. to 3,000 Pa·s or less, the adherend can be sufficiently impregnated with the crosslinkable resin composition during thermocompression bonding such as by hot pressing. , the occurrence of defects such as voids in the FRTP 12A can be suppressed, thereby improving the mechanical properties of the metal-FRTP composite member 1A. This effect is further enhanced by setting the minimum melt viscosity in the temperature range of 160 to 250° C. to 2,900 Pa·s or less, further 2,800 Pa·s or less.

The matrix resin 101 may contain, for example, natural rubber, synthetic rubber, elastomer, etc., various inorganic fillers, solvents, pigments, colorants, antioxidants, UV inhibitors, and flame retardants, as long as the adhesion and physical properties of the matrix resin 101 are not impaired. Other additives such as a retardant and a flame retardant auxiliary may be blended. Examples of elastomers that can be used include styrene-based elastomers, olefin-based elastomers, alkene-based elastomers, vinyl chloride-based elastomers, urethane-based elastomers, and amide-based elastomers. The additive is preferably blended so that the total amount of the thermoplastic resin and the reinforcing fiber 102 is 100% by volume.

The content of the thermoplastic resin contained in the matrix resin 101A is preferably 20% by volume or more and 80% by volume or less with respect to the total volume of the FRTP 12 . If the content of the thermoplastic resin is less than 20% by volume, the thermocompression bonding between the metal member 11 and the FRTP 12 will be insufficient, and there is a possibility that they will separate at the bonding surface. On the other hand, if the thermoplastic resin content exceeds 80% by volume, the softened and melted resin flows out into the mold during press working, promoting voids and defects in the CFRTP and lowering the strength of the composite material. Problems can occur. More preferably, the content of the thermoplastic resin contained in the matrix resin 101 is 35% by volume or more and 75% by volume or less. The matrix resin 101A is preferably contained so that the sum of the content of the matrix resin 101A and the content of the reinforcing fibers 102 is 100% by volume.

(Reinforcement fiber 102)
The material and reinforcing fiber base material of the reinforcing fibers 102 used in this embodiment are preferably the same as those of the reinforcing fibers 102 used in the first embodiment.

(fiber density)
Regarding the fiber density (VF: Volume Fraction) of the FRTP 12A, it is preferable that the reinforcing fibers 102 are contained in an amount of 20 to 70% by volume with respect to the total volume of the FRTP 12, as in the first embodiment. When continuous fibers are used as the reinforcing fibers 102, the VF of the FRTP 12 is preferably 40% by volume or more and 70% by volume or less, more preferably 55% by volume or more and 65% by volume or less. Further, when short fibers are used as the reinforcing fibers 102, the VF of the FRTP 12 is preferably 20% by volume or more and 50% by volume or less, more preferably 25% by volume or more and 45% by volume or less.

In the metal-FRTP composite member 1A according to this embodiment, the FRTP 12A is formed using at least one sheet of prepreg for CFRTP molding. The FRTP 12A is not limited to one layer, and may have two or more layers as shown in FIG. 7, for example. The thickness of the FRTP 12A and the number n of layers of the FRTP 12A when the FRTP 12A is formed in a plurality of layers may be appropriately set according to the purpose of use. When the FRTP 12A has multiple layers, each layer may have the same configuration or may have a different configuration. Also, the type and content ratio of the reinforcing fibers 102 constituting the FRTP 12A may differ from layer to layer.

<3.2. Processing method of metal-FRTP composite member 1A>
The structure of the metal-FRTP composite member 1A as the metal-fiber reinforced resin material composite according to the present embodiment has been described in detail above. Next, referring to FIGS. - A method for processing the FRTP composite member 1A will be described. 8 and 9 are explanatory diagrams showing examples of processing steps for the metal-FRTP composite member 1A.

The metal-FRTP composite member 1A is made by heating the FRTP 12A and the metal member 11 processed into a desired shape to a predetermined heating temperature, and then applying a predetermined pressure through a mold having a predetermined shape to integrate them. It is integrally processed through an integral processing step of processing and a mold release step of releasing the integrally processed metal member 11 and FRTP 12A from the mold at a predetermined temperature. Integral processing in the present invention means that the FRTP 12A and the metal member 11 are adhered by the matrix resin 101A, and the metal member 11 and the FRTP 12A are processed without peeling off. A method of combining (integrating) the metal member 11 and the FRTP 12A by thermocompression bonding will be described below.

<3.2.1. Method 1>
First, as shown in FIG. 8A, the FRTP 12A is arranged on at least one surface of the metal member 11 and laminated to form a laminate. In FIG. 8, similarly to the first embodiment, a mold having a convex shape is defined as an upper mold m1, and a mold having a concave shape is defined as a lower mold m2. FRTP 12 is arranged on the side. A case where the FRTP 12A is arranged above the metal member 11 is shown. At this time, it is preferable that the bonding surface of the FRTP 12A to be bonded to the metal member is activated by the same method as in the first embodiment. Moreover, it is preferable to previously remove deposits and degrease the surface of the metal member 11 by the same method as in the first embodiment. In FIG. 8(a), instead of the FRTP 12A, a prepreg for FRP molding can be laminated.

In FIG. 8A, instead of the FRTP 12A, it is also possible to integrally process the FRP molding prepreg and the metal member 11A while compositing them at the time of integral processing, which will be described later, in place of the FRTP 12A. be. It is also possible to integrally process a composite of the metal member 11A and the FRTP 12A in advance by a method to be described later. Further, the FRTP 12A is not limited to one layer as shown in FIG. 7, and may be multiple layers.

Next, as shown in FIG. 8(b), the laminate of this metal member 11 and FRTP 12A is heated to _a predetermined heating temperature T1. The heating temperature T1 is the temperature at which the FRTP itself deforms due to its own weight if it is kept at that temperature for a long time, for example, _one hour or longer, that is, the temperature at which the FRTP alone cannot retain its shape. Specifically, the heating temperature T1 is lower than the decomposition temperature of the thermoplastic resin and (Tg+50)° C. or more, where Tg is the glass transition _point of the thermoplastic resin contained in the matrix resin 101A of the FRP. The temperature is preferably in the range of (Tg+200)° C. or lower. If the heating temperature T1 is _equal to or higher than the decomposition temperature of the thermoplastic resin, the thermoplastic resin will decompose and the adhesiveness to the metal member 11 will decrease, resulting in a decrease in the strength of the metal-FRTP composite member 1A. There is The decomposition temperature in this embodiment means the temperature at which the weight loss is 1% when the thermogravimetric measurement of the resin contained in the FRTP 12 is performed in an air atmosphere. If the heating temperature T1 is _less than (Tg+50)° C., separation may occur at the interface between the metal member 11 and the FRTP 12A. In addition, when the heating temperature T1 is _less than (Tg+50)° C., the flowability of the matrix resin 101A is low. Therefore, when a plurality of layers of the FRTP 12A are laminated, shear displacement occurs between the layers of the FRTP 12A during bending. may occur. If the heating temperature T1 is higher _than (Tg+200)° C., the fluidity of the matrix resin 101A becomes too high, and the matrix resin 101A may flow out of the mold m. As a result, the matrix resin in FRTP12A may decrease and the strength of the composite may decrease. _The heating temperature T1 is more preferably (Tg+90)°C or higher and (Tg+150)°C or lower.

In order to improve the releasability of the metal-FRTP composite member 1A, the surface of the mold m may be subjected to mold release treatment and preheating of the mold m in the same manner as in the first embodiment. preferable.

Next, as shown in FIG. 8(c), using a mold m, pressure is applied to the metal member 11 and the FRTP 12A, and the metal member 11 and the FRTP 12A are processed into _a predetermined shape at the above heating temperature T1.

The press load during processing is preferably 0.1 kN or more and 100 kN or less. If it is less than 0.1 kN, it may not be possible to process the composite material of the FRTP 12 having a thickness of less than 12 mm and the steel plate having a thickness of 0.1 mm or more into a predetermined shape. On the other hand, if the press load is 100 kN, the fibers may break, which is not preferable.

The working rate of the laminate of the metal member 11 and FRP is defined by the strain rate of the material, and the range is preferably 0.05 to 10 s ⁻¹ . The strain rate of the material is the velocity of the mold m divided by the thickness of the material. If the strain rate is less than 0.05 s ⁻¹ , integral molding is possible, but the productivity drops significantly. If it exceeds 10 s ⁻¹ , the resin in the FRTP 12 cannot follow the processing of the steel sheet, and there is a possibility that the layers of the FRTP 12 will be misaligned. More preferably, the processing speed is within a range where the strain rate of the laminate of the metal member 11 and FRP is 0.5 s ⁻¹ or more and 5 s ⁻¹ or less.

If the pressing time is at least 1 minute or more, the resin in the FRTP moves to the steel plate and the adhesiveness is secured, so the integrated metal-FRTP composite member 1 can be processed, and it is 5 minutes or more. and preferred. Although there is no particular upper limit, it is preferably 10 minutes or less from the viewpoint of productivity.

Thereafter, as shown in FIG. 8(d), the pressure applied by the mold m is removed at the mold release temperature T2, and the metal-FRTP composite member 1A is obtained by removing it from the mold m.

At this time, the release temperature T2 is set so that when the FRTP alone is held at the above temperature, a minute force, for example, a force of 1 N or more is applied, so that the carbon fibers and resin in the FRTP do not crack. It is a temperature at which the shape is not fixed, that is, a predetermined temperature at which the shape is not fixed. Specifically, the heating temperature T2 is preferably a temperature within the range of (Tg+20)° C. or more and (Tg+200)° C. or less. If the release temperature T2 is less than (Tg+20)° C., the FRTP 12A cannot follow the springback of the metal member 11, and separation may occur at the interface between the metal member 11 and the FRTP 12A. Moreover, when the release temperature T2 is higher than (Tg+200)° C., the fluidity of the matrix resin 101A becomes too high, and the matrix resin 101A may flow out of the mold m. As a result, the matrix resin in FRTP12A may decrease and the strength of the composite may decrease. The release temperature T2 is more preferably (Tg+50)° C. or higher and (Tg+150)° C. or lower.

If the release temperature T2 is within the above temperature range, the resin in the FRTP 12A has fluidity that can follow the springback of the metal member 11, so the pressure removal rate from the metal-FRTP composite member 1A is particularly high. Not restricted.

The peel strength between the metal member 11 and the FRTP 12 is, as in the first embodiment, "JIS K 6854-3 Adhesive-Peel Adhesion Strength Test Method-Part 3: T-type Peel". method.

Although the case where the FRTP 12A is laminated on the metal member 11 has been described above, it is also possible to laminate and process the metal member 11 on the FRTP 12A as shown in FIG. A method of laminating the metal member 11 on the upper part of the FRTP 12A and integrally processing it will be described below with reference to FIG.

<3.2.2. Method 2>
When the metal member 11 is laminated on the upper part of the FRTP 12A and integrally processed, as shown in FIG. It is placed on the support plate b, and pressure is applied through the mold m for thermocompression bonding.

The bonding surface of the FRTP 12A to be bonded to the metal member 11 is preferably roughened by blasting or activated by plasma or corona treatment, as in the first embodiment. In addition, in FIG. 9(a), instead of the FRTP 12A, a prepreg for FRP molding can be laminated. Further, the FRTP 12A is not limited to one layer as shown in FIG. 7, and may be multiple layers.

Next, as shown in FIG. 9(b), the laminate of the FRTP 12A and the metal member 11 is placed on the support plate b and heated to _a predetermined heating temperature T1. _The heating temperature T1 at this time is the same as the heating temperature T1 of method ₁ .

In order to improve the releasability of the metal-FRTP composite member 1A, the surface of the mold m is preferably subjected to the same release treatment as in method 1. Moreover, it is preferable that the surface of the support plate b is also subjected to a release treatment similar to that of Method 1. Moreover, when heating the laminate, it is preferable to preheat the mold m by the same method as method 1.

Next, as shown in FIG. 9(c), using a mold m, a molding pressure is applied to the metal member 11, the molded body of the _FRTP 12A, and the support plate b. process. At this time, it is preferable that the shape of the mold m is such that the thickness of the support plate b is taken into consideration so that the laminate of the metal member 11 and the FRTP 12A can be the metal-FRTP composite member 1 of a desired shape. The press load, processing speed, pressure application time, etc. can be set to the same conditions as in Method 1.

After that, as shown in FIG. 9(d), the pressure applied by the mold _m is removed at the mold release temperature T2, and the composite member is removed from the mold m to obtain a metal-FRTP composite member 1A. The mold release temperature T2 at this _time is the same as the mold release temperature T2 in the _first method.

According to the present embodiment described above, the metal-FRTP composite member 1A in which the metal member 11 and the FRTP 12A are firmly joined without the step of bonding the metal member 11 and the FRTP 12A in advance or the step of shaping is required. Integrated processing becomes possible. In this method, the metal member 11 and the FRTP 12A may be pre-bonded and then integrally processed in the next step.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. The methods of testing and measuring various physical properties in the examples are as follows.

<4. First embodiment>
A crystalline resin was used as the thermoplastic resin contained in the matrix resin 101 of the FRTP 12, and the metal member 11 and the FRTP 12 were integrally processed by the previously described method 1 to prepare a specimen. Tables 1-1 and 1-2 show manufacturing conditions for each specimen.

A steel plate and an aluminum alloy plate (A5052) were used for the metal member 11 . The steel plate used had a yield stress to Young's modulus ratio of 5.5×10 −3 and a thickness of 1.5 mm. The ratio of yield stress to Young's modulus of the aluminum alloy used was 3.56×10 −3 and the thickness of the aluminum alloy was 0.6 mm. As the reinforcing fibers 102 contained in the FRTP 12, carbon fiber cloth (PAN-based carbon fiber STS60 manufactured by Toho Tenax Co., Ltd.) and unidirectional glass fibers were used. Polypropylene and nylon were used as the crystalline thermoplastic resin contained in the matrix resin 101 . As an additive in the matrix resin 101, an olefin-based elastomer (manufactured by Sumitomo Chemical Co., Ltd., Esporex TPE series) was used. As the FRTP 12 containing the unidirectional glass fiber, a glass fiber prepreg: CETEX TC960 manufactured by TENCATE, in which the matrix resin 101 is nylon, was used. The laminate obtained by laminating the FRTP 12 on the upper part of the metal member 11 is heated at the heating temperature T1 shown in Tables 1-1 and 1-2, the strain rate is set to 1 s-1, the press load is set to 50 kN, and the press This laminate was processed at a time of 5 minutes. After that, it was released from the mold m at the release temperature T2 shown in Tables 1-1 and 1-2 to obtain a composite. At this time, Daifree manufactured by Daikin Industries, Ltd. was spray-coated on the mold as a release agent.

For the samples obtained by the above method, the presence or absence of interfacial peeling between the metal member 11 and the FRTP 12 and the shear displacement of the FRTP 12 were confirmed. Regarding interfacial peeling between the metal member 11 and the FRTP 12, the interface between the metal member 11 and the FRTP 12 was observed using an optical microscope (manufactured by Keyence Corporation, VH-5500), and no interfacial peeling of 50 μm or more was observed. was evaluated as very good (⊚), those in which peeling of 100 μm or more was not confirmed were evaluated as good (◯), and those in which peeling of 100 μm or more was confirmed were evaluated as disqualified (×).

Regarding the shear displacement of FRTP12, the surface of FRTP12 of the sample obtained by processing was observed, and when no protrusions of 100 µm or more were observed, it was rated as very good (⊚), and when no protrusions of 500 µm or more were observed, it was rated as good ( ○), and those in which protrusions of 500 μm or more were confirmed were rejected (x).

Moreover, the peel strength test was performed by the following method. A test piece having a width of 15 mm and a length of 90 mm is cut from the prepared sample, the metal member 11 of the test piece is peeled off from the FRTP 12 by 30 mm, and only the metal portion is bent at 90 degrees. On the surface of the FRTP 12 opposite to the surface to which the metal member 11 is bonded, a room temperature curing adhesive is used to bond a metal member bent at 90 degrees. A test piece prepared as described above can be used for a peel strength test. In addition, when the adhesive strength between the room temperature curing adhesive used and the FRTP 12 was separately examined, it was 200 N or more, so this peel strength test result reflects the peel strength between the metal member 11 and FRTP 12. becomes.

As shown in Tables 1-1 and 1-2, after integrally processing the metal member 11 and the FRTP 12 by setting the heating temperature T1 within the temperature range of (Tm-20) ° C. to (Tm + 10) ° C. , By setting the release temperature T2 within the temperature range of (Tm-30) ° C. to (Tm + 10) ° C. and releasing the metal-FRTP composite member 1 from the mold, excellent moldability and workability It was found that a metal-FRTP composite member 1 was obtained. It was also found that the metal-FRTP composite member 1 obtained by the processing method according to this embodiment exhibits a peel strength of 20 N or more.

<5. Second embodiment>

An amorphous resin is used as the thermoplastic resin contained in the matrix resin 101A of the FRTP 12A, and the metal member 11 and the FRTP 12A are integrally processed by applying the method 1 of the second embodiment described above to prepare a specimen. bottom. Tables 2-1 to 2-3 show manufacturing conditions for each specimen.

A steel plate, an aluminum plate, and an aluminum alloy plate (A5052) were used for the metal member 11 . The steel plate used had a yield stress-to-Young's modulus ratio of 5.5×10 ⁻³ and a thickness of 1.5 mm. The aluminum plate used had a yield stress-to-Young's modulus ratio of 1.0×10 ⁻³ and a thickness of 0.5 mm. The aluminum alloy used had a yield stress-to-Young's modulus ratio of 3.56×10 ⁻³ and a thickness of 0.6 mm. As the reinforcing fibers 102 contained in the FRTP 12, carbon fiber cloth (PAN-based carbon fiber STS60 manufactured by Toho Tenax Co., Ltd.) and unidirectional glass fibers were used. Polypropylene and nylon were used as the crystalline thermoplastic resin contained in the matrix resin 101 . As an additive in the matrix resin 101, an olefin-based elastomer (manufactured by Sumitomo Chemical Co., Ltd., Esporex TPE series) was used. As the FRTP 12 containing the unidirectional glass fiber, a glass fiber prepreg: CETEX TC920 manufactured by TENCATE, in which the matrix resin 101 is polycarbonate, was used. The laminate obtained by laminating the FRTP12A on the upper part of the metal member 11 is heated at the heating temperature T ₁ shown in Tables 2-1 to 2-3, the strain rate is 1 s ^-1 , the press load is set to 50 kN, This laminate was processed with a press time of 5 minutes. After that, it was released from the mold m at the release temperature T2 shown in Tables 2-1 to _2-3 to obtain a composite. At this time, Daifree manufactured by Daikin Industries, Ltd. was spray-coated on the mold as a release agent.

For the samples obtained by the above method, the presence or absence of interfacial peeling between the metal member 11 and the FRTP 12A and shear displacement of the FRTP 12A were confirmed. Regarding the interfacial peeling between the metal member 11 and the FRTP 12A, the interface between the metal member 11 and the FRTP 12A was observed using an optical microscope (manufactured by Keyence Corporation, VH-5500), and no interfacial peeling of 50 μm or more was observed. was rated as very good (⊚), those in which peeling of 100 μm or more was not confirmed were rated as good (◯), and those in which peeling of 100 µm or more was confirmed were rated as disqualified (×).

Regarding the shear displacement of FRTP12A, the surface of the sample FRTP12A obtained by processing was observed, and when no protrusions of 100 µm or more were observed, it was rated as very good (⊚), and when no protrusions of 500 µm or more were observed, it was rated as good ( ○), and those in which protrusions of 500 μm or more were confirmed were rejected (×).

Moreover, the peel strength test was performed by the following method. A test piece having a width of 15 mm and a length of 90 mm is cut from the prepared sample, the metal member 11 of the test piece is peeled off from the FRTP 12A by 30 mm, and only the metal portion is bent at 90 degrees. On the surface of the FRTP 12A opposite to the surface to which the metal member 11 is bonded, a room temperature curing adhesive is used to bond a metal member bent to 90 degrees. A test piece prepared as described above can be used for a peel strength test. In addition, when the adhesive strength between the room temperature curing adhesive used and the FRTP 12 was separately examined, it was 200 N or more, so this peel strength test result reflects the peel strength between the metal member 11 and FRTP 12. becomes.

As shown in Tables 2-1 to 2-3, the heating temperature T1 is set to less than 400 ° C. and within a temperature range of (Tg + 50) ° C. or higher and (Tg + 200) ° C. or lower, and the metal member 11 and FRTP 12A After integral processing, the metal-FRTP composite member 1A is released from the mold by setting the release temperature T2 to a temperature range of less than 400 ° C. and within a temperature range of (Tg + 20) ° C. to (Tg + 200) ° C. It was found that a metal-FRTP composite member 1A having excellent moldability and workability can be obtained. It was also found that the metal-FRTP composite member 1A obtained by the processing method according to this embodiment exhibits a peel strength of 20 N or more.

Although the preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, the present invention is not limited to such examples. It is obvious that a person having ordinary knowledge in the technical field to which the present invention belongs can conceive of various modifications or modifications within the scope of the technical idea described in the claims. It is understood that these also naturally belong to the technical scope of the present invention.

1, 1A metal-FRTP composite member 11 metal member 12, 12A FRTP
101, 101A matrix resin 102 reinforcing fiber

Claims (7)

After heating a metal plate having a matrix resin containing a thermoplastic resin and a fiber reinforced resin material having a reinforcing fiber material on at least one surface thereof to a predetermined temperature at which the fiber reinforced resin material alone cannot retain its shape, an integral processing step of applying a predetermined pressure through a mold having a predetermined shape to integrally process the mold into a shape that follows the predetermined shape of the mold;
a mold release step of releasing the integrally processed metal plate and the fiber reinforced resin material from the mold at a predetermined temperature at which the shape of the fiber reinforced resin material is not completely determined,
The thermoplastic resin is an amorphous resin other than polycarbonate having a glass transition temperature Tg,
The heating temperature in the integral processing step is lower than the decomposition temperature of the amorphous thermoplastic resin and is in the temperature range of (Tg + 50) to (Tg + 200) ° C.,
The release temperature in the release step is a temperature lower than the decomposition temperature of the amorphous thermoplastic resin and in the temperature range of (Tg + 20) to (Tg + 200) ° C. ,
The amorphous thermoplastic resin contains one selected from phenoxy resin, polymethyl methacrylate, polystyrene, amorphous polyarylate, and polysulfone,
A metal-thermoplastic fiber reinforced resin material composite member processing method. The thermoplastic resin is contained in an amount of 20 to 80% by volume with respect to the total volume of the fiber reinforced resin material, and the total of the reinforcing fiber material and the matrix resin is 100% by volume.
The method for processing the metal-thermoplastic fiber reinforced resin material composite member according to claim 1. The reinforcing fiber material is contained in an amount of 20 to 70% by volume with respect to the total volume of the fiber-reinforced resin material, and the total amount of the reinforcing fiber material and the matrix resin is 100% by volume.
The method for processing the metal-thermoplastic fiber reinforced resin material composite member according to claim 1 or 2. The thickness of the metal plate is 0.1 to 6.0 mm, and the ratio of the yield stress to the Young's modulus of the metal plate is 0.8 × 10 ^-3 or more.
The method for processing the metal-thermoplastic fiber reinforced resin material composite member according to any one of claims 1 to 3. The material of the metal plate is a steel material,
The method for processing the metal-thermoplastic fiber reinforced resin material composite member according to any one of claims 1 to 4. The reinforcing fiber material is a carbon fiber material,
The method for processing the metal-thermoplastic fiber reinforced resin material composite member according to any one of claims 1 to 5. A predetermined release treatment is applied to the surface of the mold,
The method for processing the metal-thermoplastic fiber reinforced resin material composite member according to any one of claims 1 to 6.

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